Ozone, atmosphere formation

Wolkoff, P., Clausen, P.A., Wilkins, C.K., Hougaard, K.S. and Nielsen, G.D. (1999) Formation of strong airway irritants in a model mixture of (+)-alpha-pinene/ozone. Atmospheric Environment, 33, 693-8. 

Ozone is a natural constituent of the upper atmosphere trace amounts naturally exist in the lower atmosphere. Formation of 03 in the upper atmosphere occurs in steps, i.e., a molecule of oxygen being split into atomic oxygen and the resulting atomic oxygen reacting with another oxygen molecule to form ozone ... 

At that time, nothing was known about the atmospheric formation reactions of O3 and H2O2 and which chemical mechanisms existed between both species in the gas and aqueous phases. The formation of ozone, hydrogen peroxide and nitric acid in air had been attributed generally to variations in the electrical condition of the atmosphere" (Fox 1873). The period 1850-1880 of uncounted ozone measurements using the Schonbein paper has often been criticized, and it is likely that apart from ozone, nitrous acid and hydrogen peroxide were also responsible for the blue... 

The widest application of PTR-MS is in the field of atmospheric monitoring. In air, VOCs originate from diverse sources but primarily from biogenic origin. Many VOCs have effects on the sources and sinks of ozone, aerosol formation, and climate change. In addition, some VOCs are also toxic to human beings [34], so it is important to monitor their concentrations in wider environments. Nowadays, PTR-MS has been used to detect VOCs from plants, forest, and human activities. 

More precisely, the rate of ozone formation depends closely on the chemical nature of the hydrocarbons present in the atmosphere. A reactivity scale has been proposed by Lowi and Carter (1990) and is largely utilized today in ozone prediction models. Thus the values indicated in Table 5.26 express the potential ozone formation as O3 formed per gram of organic material initially present. The most reactive compounds are light olefins, cycloparaffins, substituted aromatic hydrocarbons notably the xylenes, formaldehyde and acetaldehyde. Inversely, normal or substituted paraffins. 

Emissions from methanol vehicles are expected to produce lower HC and CO emissions than equivalent gasoline engines. However, methanol combustion produces significant amounts of formaldehyde (qv), a partial oxidation product of methanol. Eormaldehyde is classified as an air toxic and its emissions should be minimized. Eormaldehyde is also very reactive in the atmosphere and contributes to the formation of ozone. Emissions of NO may also pose a problem, especiaHy if the engine mns lean, a regime in which the standard three-way catalyst is not effective for NO reduction. 

Most ozone is formed near the equator, where solar radiation is greatest, and transported toward the poles by normal circulation patterns in the stratosphere. Consequendy, the concentration is minimum at the equator and maximum for most of the year at the north pole and about 60°S latitude. The equihbrium ozone concentration also varies with altitude the maximum occurs at about 25 km at the equator and 15—20 km at or near the poles. It also varies seasonally, daily, as well as interaimuaHy. Absorption of solar radiation (200—300 nm) by ozone and heat Hberated in ozone formation and destmction together create a warm layer in the upper atmosphere at 40—50 km, which helps to maintain thermal equihbrium on earth. 

Because of the expanded scale and need to describe additional physical and chemical processes, the development of acid deposition and regional oxidant models has lagged behind that of urban-scale photochemical models. An additional step up in scale and complexity, the development of analytical models of pollutant dynamics in the stratosphere is also behind that of ground-level oxidant models, in part because of the central role of heterogeneous chemistry in the stratospheric ozone depletion problem. In general, atmospheric Hquid-phase chemistry and especially heterogeneous chemistry are less well understood than gas-phase reactions such as those that dorninate the formation of ozone in urban areas. Development of three-dimensional models that treat both the dynamics and chemistry of the stratosphere in detail is an ongoing research problem. 

Control of nitrogen oxides ia aircraft exhaust is of increa sing concern because nitrogen oxides react with ozone ia the protective layer of atmosphere which exists ia the altitude region where supersonic aircraft operate. Research is under way to produce a new type of combustor which minimizes NO formation. It is an essential component of the advanced propulsion unit needed for a successflil supersonic transport fleet. 

Fenner (11) has pointed out that short-lifetime constituents of the atmosphere such as nitrogen oxides, carbon monoxide, and nonmethane hydrocarbons may also play roles related to global warming because of their chemical relations to the longer-lived greenhouse gases. Also, SO, with a very short life interacts with ozone and other constituents to be converted to particulate sulfate, which has effects on cloud droplet formation. 

Reaction (12-9) shows the photochemical dissodation of NO2. Reaction (12-10) shows the formation of ozone from the combination of O and molecular O2 where M is any third-body molecule (principally N2 and O2 in the atmosphere). Reaction (12-11) shows the oxidation of NO by O3 to form NO2 and molecular oxygen. These three reactions represent a cyclic pathway (Fig. 12-4) driven by photons represented by hv. Throughout the daytime period, the flux of solar radiation changes with the movement of the sun. However, over short time periods (—10 min) the flux may be considered constant, in which case the rate of reaction (12-9) may be expressed as... 

Environmental Fate. A portion of releases of toluene to land and water will evaporate. Toluene may also be degraded by microorganisms. Once volatilized, toluene in the lower atmosphere will react with other atmospheric components contributing to the formation of ground-level ozone and other air pollutants. 

In densely populated areas, traffic is responsible for massive exhausts of nitrous oxides, soot, polyaromatic hydrocarbons, and carbon monoxide. Traffic emissions also markedly contribute to the formation of ozone in the lower parts of the atmosphere. In large cities, fine particle exposure causes excess mortality which varies between one and five percent in the general population. Contamination of the ground water reservoirs with organic solvents has caused concern in many countries due to the persistent nature of the pollution. A total exposure assessment that takes into consideration all exposures via all routes is a relatively new concept, the significance of which is rapidly increasing. 

P. Crutzen (Max Planck Institute for Chemistry, Mainz), M. Molina (Massachusetts Institute of Technology) andF. S. Rowland (Irvine, California) work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone. 

One strategy in limiting the formation of ozone and other photochemical oxidants has been the use (in the past) of low reactivity fuels in internal combustion engines. More recently, alternate fuels (methanol, for instance) have been proposed for regions that suffer from elevated levels of photochemical air pollution. The effect of switching to such a low-reactivity fuel may be seen in Equation E2 for methanol, which has a simple atmospheric reaction mechanism. 

CO to CO2 (e.g. Finlayson-Pitts and Pitts 1986). The role of HOj in any of these atmospheric cleansing and oxidant formation pathways is a catalytic one, but the generation of ozone is strongly dependent upon the nitric oxide concentration. 

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